Insights into Hydrogen Gas Environment-Promoted Nanostructural Changes in Stressed and Relaxed Palladium by Environmental Transmission Electron Microscopy and Variable-Energy Positron Annihilation Spectroscopy.

Abstract

Environmental transmission electron microscopy (ETEM) and variable-energy positron annihilation spectroscopy (VEPAS) are used to observe hydrogen-induced microstructural changes in stress-free palladium (Pd) foils and stressed Pd thin films grown on rutile TiO2 substrates. The microstructural changes in Pd strongly depend on the hydrogen pressure and on the stress state. At room temperature, enhanced Pd surface atom mobility and surface reconstruction is seen by ETEM already at low hydrogen pressures ( pH < 10 Pa). The observations are consistent with molecular dynamics simulations. A strong increase of the vacancy density was found, and so-called superabundant vacancies were identified by VEPAS. At higher pressures, migration and vanishing of intrinsic defects is observed in Pd free-standing foils. The Pd thin films demonstrate an increased density of dislocations with increase of the H2 pressure. The comparison of the two studied systems demonstrates the influence of the mechanical stress on structural evolution of Pd catalysts.